Dyeing of mixed textile materials



United ates Patent 2,893,812 DYEING F MIXED TEXTILE-'MATER IALS Yves Henri Gnyonnet, VilIefranche-sur Saone (Rhone), France, assignor to Societe Rhodiaceta, Paris, France, a corporation of France No Drawing. Application December 2, 1955 Serial No. 550,782 Claims priority, application France Decemberv 8, 1954 19 Claims. (Cl.8'24) invention relates toth'e dyein'g of-mixed textile materials and more particularly to the level dyeing of textile materials containing :polyac'rylonitrile fibres (as herein defined) and cellulose derivative fibres, with watersoluble dyestuffs, acid dyes, direct dyes and soluble dyes for cellulose acetate.

By p'olyacrylonitrile fibres are meant'those produced from polyacrylonitrile or 'co-polymers of aorylonitrile ..Wlth other polymerisable monomers containing at least 85% of acrylonitrile in their molecule, or from mixtures of these polymers withother vinyl polymers. Specific fibres of these types are those made from 1) polyacry- --l onit'r-ile;(2) co-poly'inersof acrylonitrile with vinyl chlo- "ride, vinyl acetate, vinylidene chloride, vinylidene cyastuffs are applied to textile articles containing both'cellulose derivative fibres and polyacrylonitrile fibres, their affinity for the different fibres is so different that they dye almost exclusively the cellulose derivative fibres. It has heretofore been impossible therefore to eifect by the known processes a level'dyeing of these two types of fibres y when they are mixed in a textile material.

It is known that -polyacrylonitrile fibres can bedyed-by means of water-soluble dyes in the presence of cuprons salts [Rayon and Synthetic Textiles, 31, 35 (1950-); Chemical and Engineering News, 28, 4268 (1950)], but this process is not suitable for dyeing mixtures of fibres containingbo'th polyacrylonitrile fibres and other fibres.

According to the present invention a process for the I level dyeing of textile materials containing both cellulose "derivative fibres and polyacrylonitrile fibres comprises applying to or incorporating in the cellulose derivative fibres a colourless organic nitrogenous compound having an afiinity therefor, and simultaneously or subsequently dyeing the textile materials with water-soluble dyestufis in the presence'of cuprous ions.

The textile'materials may be in a-riyform, e.g. filaments, fibres, loose fibre, cabled yarns, union yarns, staple fibre yarns, tows, slivers, woven or knitted fabrics, or pre-formed textile garments-or the like. The water- 'soluble dyestufis maybe acid dyes, direct dyesor watersoluble dyes for-cellulose acetate.

The aflinity of a nitrogenous organic compound'for a textile materialis defined by the extent to which the compound is extracted by-the said textile material from an aqueous bath in which 'iUiSjPI'CSflDI in the formot aso;

2,893,812 Fiatented July 7, 1 959 2 lution (true or colloidal), an emulsion or a suspension. In practice, a compound may .b-e-regardedas'havin'g an afiinityfor cellulose derivativefibres whemfor-example, 2O grammes of cellulose derivative fibrespresentin an aqueous bath containing 1 g;/ litre "of the-'compoundatg80" C. extract and retain at least 25% of the 'conipound 'from the bath. Products suitable for carrying outthepresent invention are, for example, saturated 'he't'erocyclic coinpoundshaving 3 to 7 members in the ring, including a 'si'ngl'e i nitrogen atom, cycloaliphatic am'ines, amides obtained by condensation of aliphatic monoacids, the'chain of which contains at least "12 carbon atoms,'with a"polymethylene diamine, and the'comple'xes of'these. various compounds. There may be "mentioned, for example,

bis 4:4 '(cyanoethylamino)dicyclohexylmethane, cy-

anoethyl spirocyclohexyl ethylene imine, piperidine, bis 4:4'- (monoaminopropylamino)dicyclohexylmethane, cyanoethylaminocyclohexane, cyanoethylaminoethylcyclohexane and dyanomethylhexamethylene-imine, the complexes of these products, in particular the formaldehydebisulphite complexes and the monoacyl'amides'of Jpolymethylenediamines. These compounds may, if desired, be previously introduced in known manner into the cellulose derivatives before or duringtheir "shaping in the form of filaments. Mixed textilem'aterials containing both cellulose derivative fibrescontaining these"coinpounds and polyacrylonitrile fibres constitute novel textile materials capable of being uniformly dyed with-watersoluble dyestuifs in the presence of cuprous ions.

When the nitrogenous compoundsare applied by' -pr'etreatment of the cellulose derivatives,the textile material may-be treated, for example, by means of a bath containing from 2% to 15% of the nitrogenous compound, calculated on the weightof the said textile material, depending upon the desired'dep't'h of'dye'ing. From"0.2*to .1 g. per litre of a wetting agentmay be added to this bath if desired. The temperature of the pre treatmentinay vary from 50 to C. andits optimum duration will depend upon the temperature and can readily be determined by simple tests. The dyeing of the pre-treated textile-mate'rial may then'be'carried'out inone or'two baths, as requi'red. It is also possible to introduce the nitrogenous compound into the dyeing bath containing the desired content of dyestuif or'dyestulfs 'for producing the desired depth of dyeing'and a sufiicient quantity'of acid'to bring the pH of the 'bath to about 3-4; the said bathalso contains, or there may subsequently be added thereto, from 2% to 10% of eupric sulphate and from 0.8% to 4% of an appropriate reducing agent (e.g. metallic copper) for reducing the copper sulphate to the c'upro'us state. If desired, from 0.2 g. to 1 g. per litre of an-acid-resisting wetting agent may also'be added.

The process according to the invention affords the great advantage of permitting level dyeing in a single bath 'of I textile materials containing ditferent fibres as aforesaid and the 'dye'ings obtained have excellent 'fastness.

The followingexamples will 'serve to illustrate the invention but are not to be regarded as "limiting it "any way; the percentages are-expressed by weight relation to the fabric, and the dyestuffs are cited with reference either to Colour Index (Cl) or to Technical Manual and Year Book of the American Association; of'Textile Chemists and Colorists (prototype number: PL).

Exam'plei 1 p A fabric containing both cellulose acetate threads and polyacrylonitrile thre'adsflis :immersed' in 50- timefsfiits weight of abath containing:

10% of formaldehyde-bisulphite complex-of bis-4:4- (cyanoethylamino)--dicyclohexylniethane, f 0.2 g. per litre of'a wetting agent.

' The fabric is then rinsed and introduced into 50 times its weight of a bath containing:

% of Anthraquinone Blue SWF, 150% concentration --(-Pr.12).'

0.6% oRocel1ineS'(C.I. 176),

31cc. per litre of acetic acid.

After an hour's treatment at boiling point, there are v;

added to the bath:

10% of copper sulphate (pentahydrate), 4%. of sodium formaldehyde snlphoxylate,

in a bath at 40 C. containing 0.2 g. per litre of a condensate of ethylene oxide and oleocetyl alcohol. A royal blue fabric of very level appearance is obtained.

Example II The same fabric in Example I, having undergone the and the dyeing is continued for 30 minutes at boiling point in this bath. The fabric is rinsed and then immersed for 10 minutes same ,pre-treatment, is dipped into 50 times its weight of a bath containing:

0.1% of Anthraq-uinone Blue SWF, 150% concentration (Pr. 12),

0.6% of metanil yellow (Cl. 138),

0.25% of Rocelline S (Cl. 176),

3 cc. per litre of acetic acid.

Alfter boiling for one hour, there are added to the bath:

2% of copper sulphate (pentahydrate), 0.08% of hydroxylamine sulphate,

and the dyeing is continued for 30 minutes at boiling point.

The fabric is thoroughly rinsed and immersed for 10 minutes in a bath at 40 C. containing 0.2 g. per litre of a condensate of ethylene oxide and an alkyl phenol.

Example 111 Discontinuous polyacrylonitrile fibres and discontinuous ethyl cellulose fibres, the latter containing 8% of its weight of cyanoethylspirocyclohexyl-ethylene-imine introduced during the manufacture of the fibres, are intimately mixed in equal proportions and spun together. The yarns and fabrics obtained'with this mixed material may be dyed with a very satisfactory level effect by acid or soluble dyestufis in the presence of cuprous ions.

Example IV After boiling for 30 minutes there are added:

3 cc. per litre of acetic acid. I

The boiling is continued for 30 more minutes, whereafter there are introduced:

10% of copper sulphate (pentahydrate) 4% of hydroxylamine sulphate.

The boiling is maintained for 30 more minutes and the article is rinsed, and dried. .A very level blue-dyeing is obtained.

4 Example V The same fabric as in Example I, having undergone the same treatment with the formaldehyde-bisulphite complex of bis-4:4'-(cyanoethylamino)dicyclohexylmethane, is dipped into 50 times'its weight of a bath containing:

1% vofjaune Solacet solide GS (commercial .watersoluble dyestufi for cellulose acetate), v 1% of bleu Solacet solide 2B8 (commercial watersoluble dyestufi for cellulose acetate), 3 cc. per litre of acetic acid.

After treatment for 1 /2 hours at boiling point, there are added to the bath:

10% of copper sulphate (pentahydrate),

4% of hydroxylamine sulphate,

and the dyeing is continued for 30 minutes at point. 1

The article is thoroughly rinsed and a very level greendyed fabric is obtained.

' Example VI The same fabric as in Example I is introduced into 50 times its Weight of a bath containing:

5% of formaldehyde-bisulphite complex of bis-4:4-

(cyanoethylamino)dicyclohexylmethane, I 0.2 g. per litre of a wetting agent. I

After treatment for one hour at C. the fabric is rinsed and then introduced into 50 times its weight of; a bath containing: a

5% 'of Anthraquinone Blue SWF, concentration v(Pr. 12),

0.6% of Rocelline S (Cl. 176),

0.2 g per litre of a wetting agent,

3 cc. per litre of acetic acid,

10% of copper sulphate (pentahydrate),

4% of hydroxylamine sulphate.

The dyeing is carried out in this bath for one hour at boiling point. The article is thoroughly rinsed and a very level royal blue fabric is obtained.

Example VII.

The same fabric as in ExampleI is introduced times its weight of a bath containing:

into 50 5% of the monamide obtained by the condensation of stearic acid and trimethylene-diamine, 0.2 g. per litre of a wetting agent.

After treatment for one hour at 80 C. thefabric is rised and then introduced into 50 times its weight ofa bath containing:

1.8% of Orangell (Cl. 151),

0.35% of Rocelline S (Cl. 176),

1.15% of Anthraquinone Blue SWF, 150% concentration (Pr. 12).

After treatment for one hour at boiling point, there are added to the bath:

10% of copper sulphate (pentahydrate), 4% of hydroxylamine sulphate,

and the dyeing is continued for 30 minutes at boiling point. The article is thoroughly rinsed and a very level brown fabric is obtained.

Example VIII The same fabric as in Example I is introduced into 50 times its weight of a bath containing:

5% of the formaldehyde-bisulphite complex of bis-4:4-

(cyanoethylamino) dicyclohcxylmethane, 0.2 g. per litre of a wetting agent.

After treatment for one hour at 80 C. the fabric is rinsed and then introduced into 50 times its weight of a bath containing:

0.1% of Anthraquinone Blue SWF, 150% concentration 0.25% of Rocelline S (Cl. 176),

0.6% of metanil yellow (0.1. 138),

2% of copper sulphate (pentahydrate),

A copper plate,

3 cc. per litre of acetic acid.

The dyeing is carried out in this bath for one hour at boiling point. The article is thoroughly rinsed and a very level grey-green fabric is obtained.

I claim:

1. A process for the level dyeing of textile materials containing both fibres of a cellulose derivative selected from the class consisting of the water-insoluble esters and others of cellulose and fibres of an acrylonitrile polymer selected from the class consisting of acrylonitrile homopolymer and copolymers of acrylonitrile with other vinyl compounds copolymerisable therewith, which copolymers contain at least 85% of acrylonitrile units, which comprises incorporating in said cellulose derivative fibres a colourless organic nitrogenous monomeric compound selected from the group which conssists of (1) saturated heterocyclic compounds having 3-7 members in the ring, of which one is a single nitrogen atom, (2) cycloaliphatic amines, (3) amides obtained by the condensation of an aliphatic monocarboxylic acid having at least 12 carbon atoms in the chain with a polymethylene diamine, and (4) complexes of these compounds.

2. Process according to claim 1, wherein there is incorporated in the cellulose derivative fibres a compound selected from the group consisting of bis-4:4-(cyanoethylamino)-dicyclohexylmethane, its formaldehyde bisulphite complex, cyanoethyl-spirocyclohexyl-ethyleneimine and stearic acid 3-aminopropylamide.

3. Process according to claim 1 wherein the cellulose derivative is cellulose acetate.

4. Process according to claim 3, wherein there is incorporated in the cellulose acetate fibres a compound selected from the group which consists of bis-4:4-(cyanoethylamino)-dicyclohexylmethane, its formaldehyde bisulphite complex, cyanoethyl-spirocyclohexyl-ethyleneimine and stearic acid 3-aminopropylamide.

5. Process according to claim 3, wherein stearic acid B-aminopropylamide has been incorporated in the cellulose acetate fibres during their manufacture.

6. Process according to claim 1, which comprises incorporating bis 4:4 (cyanoethylamino) dicyclohexylmethane in the textile material by treating the material with an aqueous bath containing 2-15% thereof, based on the weight of the textile material.

7. Process according to claim 6, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

8. Process according to claim 1, which comprises incorporating the formaldehyde bisulphite complex of 6 bis-4:4'-(cyanoethylamino)-dicyclohexylmethane in the textile material by treating the material with an aqueous bath containing 2-15% thereof, based on the weight of the textile material.

9. Process according to claim 8, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

10. Process according to claim 1, which comprises incorporating stearic acid 3-aminopropylamide in the textile material by treating the material with an aqueous bath containing 2-15 thereof, based on the weight of the textile material.

11. Process according to claim 10, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

12. Process according to claim 1, wherein cyanoethylspirocyclohexyl-ethylene-imine has been incorporated in the cellulose derivative fibres during their manufacture.

13. Process according to claim 12, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

14. Process according to claim 1, which comprises dyeing the textile material with a dyebath containing a watersoluble dyestufr, cuprous ions, and 2-15%, by weight of the textile fabric, of bis-4:4'-(cyanoethylamino)-dicyclohexylmethane.

15. Process according to claim 14, wherein the textile material contains both" cellulose acetate fibres and fibres of the said acrylonitrile polymer.

16. Process according to claim 1, which comprises dyeing the textile material with a dyebath containing a water-soluble dyestufi, cuprous ions, and 2-15%, by weight of the textile fabric, of the formaldehyde bisulphite complex of bis-4:4'-(cyanoethylamino)-dicyclohexylmethane.

17. Process according to claim 16, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

18. Process according to claim 1, which comprises dyeing the textile material with a dyebath containing a water-soluble dyestuff, cuprous ions, and 2-15%, by weight of the textile fabric, of stearic acid 3-aminopropylam e.

19. Process according to claim 18, wherein the textile material contains both cellulose acetate fibres and fibres of the said acrylonitrile polymer.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Technical Bulletin by du Pont, vol. 7, No. 1, March 1951, pp. 45, 46 and 52. 

1. A PROCESS FOR THE LEVEL DYEING OF TEXTILE MATERIALS CONTAINING BOTH FIBRES OF A CELLULOSE DERIVATIVE SELECTED FROM THE CLASS CONSISTING OF THE WATER-INSOLUBLE ESTERS AND ETHERS OF CELLULOSE AND FIBRES OF AN ACRYLONITRIE POLYMER SELECTED FROM THE CLASS CONSISTING OF ACRYLONITRILE HOMOPOLYMER AND COPOLYMERS OF ACRYLONITRILE WITH OTHER VINYL COMPOUNDS COPOLYMERS OF ACRYLONITRILE UNITS, POLYMERS CONTAIN AT LEAST 85% OF CRYLONITRILE UNITS WHICH COMPRISES INCORPORATING IN SAID CELLULOSE DERIVATIVE FIBRES A COLOURLESS ORGANIC NITROGENOUE MONOMERIC COMPOUND SELECTED FROM THE GROUP WHICH CONSISTS OF (1) SATURATED HETEROCYCLIC COMPOUNDS HAVING 3-7 MEMBERS IN THE RING, OF WHICH ONE IS A SINGLE NITROGEN ATOM, (2) CYCLOALIPHATIC AMINES, (3) AMIDES OBTAINED BY THE CONDENSATION OF AN ALIPHATIC MONOCARBOXYLIC ACID HAVING AT LEAST 12 CARBON ATOMS IN THE CHAIN WITH A POLYMETHYLENE DIAMINE, AND (4) COMPLEXES OF THESE COMPOUNDS. 